Activation of the Ga(I) cation for bond activation: from oxidative additions into C−Cl and H−P bonds to reversible insertion into P4
Abstract: Although the discovery of the GaI complex salt [Ga(PhF)2-3][Al(ORF)4] (RF=C(CF3)3, PhF=C6H5F) invoked the preparation of a diverse library of cationic Ga(I) coordination complexes and clusters, studies on small molecule activation with low-valent GaI cations are scarce. Herein, a first experimental study on the reactivity of a monomeric Ga(I) cation activated with a pyridine–diimine pincer ligand (in [Ga(PDIdipp)][Al(ORF)4]) towards small-molecules is reported. First controlled oxidative additions of the GaI cation into C−Cl, H−P and P−P bonds are presented. Moreover, the [4+1]cycloaddition to butadienes was achieved. Intriguingly, the isolated, blue insertion product into the P−P bond of P4 allows for the quantitative release of the P4 molecule upon reaction with AlEt3 and butadienes. Reversible P4 insertion of main-group metals has previously been reported for Ge and Sn, respectively. The experimental study is supported by high-level computational analysis of the in-part reversible oxidative additions at the DLPNO-CCSD(T)/def2-TZVPP//PBEh-3c/def2-mSVP level of theory with COSMO-RS solvation in 1,2-difluorobenzene
- Standort
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Deutsche Nationalbibliothek Frankfurt am Main
- Umfang
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Online-Ressource
- Sprache
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Englisch
- Anmerkungen
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Chemistry – a European journal. - 29, 58 (2023) , e202302212, ISSN: 1521-3765
- Ereignis
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Veröffentlichung
- (wo)
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Freiburg
- (wer)
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Universität
- (wann)
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2023
- Urheber
- DOI
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10.1002/chem.202302212
- URN
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urn:nbn:de:bsz:25-freidok-2386957
- Rechteinformation
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Letzte Aktualisierung
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25.03.2025, 13:55 MEZ
Datenpartner
Deutsche Nationalbibliothek. Bei Fragen zum Objekt wenden Sie sich bitte an den Datenpartner.
Beteiligte
- Dabringhaus, Philipp
- Heizmann, Tim
- Krossing, Ingo
- Universität
Entstanden
- 2023
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